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  • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
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  • C01B21/0622—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with iron, cobalt or nickel
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  • C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
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  • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
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  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
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  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams

Definitions

• the present invention is to be associated with the material system of carbon, nitrogen, hydrogen and transition metal with respect to the input materials as well as the reaction conditions.
• the material system C, N, H is reported.
• Examinations in the material system C, N, H, transition metal focus on the production of nitrides and carbides of some transition metals as well as on the synthesis of incorporation compounds, in which the transition metal is in a graphitic carbon nitride structure constructed of planar s-triazine units.
• Many methods known from the prior art for producing carbon nitrides involve pyrolysis of chemical substances and/or substance mixtures. DING, Z.
• the present invention is based on the object to provide a method for producing transition metal compounds of the initially mentioned kind, which allows the inexpensive production of a starting material for producing economically interesting valuable materials, in particular valuable materials containing carbon and nitrogen having cubic phases. Further, it is the object of the present invention to provide a correspondingly produced transition metal compound.
• the invention is based on the realization that in heat treatment in a first temperature range between 150° C. and 570° C., in particular between 300° C.
• first temperature range between 150° C. and 570° C.
• Transition metal compounds produced according to the method according to the invention contain di-imino-tri-s-triazine as a component. Only with the mentioned high proportion of transition metal in the reaction mixture, the formation of metal clusters is allowed, the supply of delocalized electrons of which in the condensation of the non-condensed or only slightly condensed C—N—H compounds such as for example melamine or dicyandiamide or cyanamide entails the formation and stabilization of compounds, in which di-imino-tri-s-triazine tautomers exist bound to transition metals. The formation of graphitic structures in the use of the transition metal compounds according to the invention is reliably prevented.
• the transition metal compounds according to the invention can serve for producing economically interesting valuable materials, in particular valuable materials containing carbon and nitrogen, having cubic phases.
• the transition metal compounds according to the invention have a metal carbide structure, for example an X-ray diffractogram comparable to the nickel carbide for example in using nickel. They are only obtained in the conversion of reaction mixtures with high transition metal contents, i.e. at least 6 mole percent, preferably 10 to 40 mole percent, related to the reaction mixture.
• the Bragg reflections of the X-ray powder diagrams of the transition metal compounds according to the invention prove the presence of materials present in a crystal lattice analogous to the metal carbide, for example the nickel carbide.
• Ni 3 C nickel carbide Ni 3 C
• the molar ratio of transition metal and/or transition metal compound to the slightly condensed C—N—H compounds is advantageously each between 1:2 and 1:8.
• the heat treatment can be performed in one-stage or multi-stage manner or in alternating manner within the first temperature range. Furthermore, there is the possibility that the heat treatment is performed within the first temperature range over a period of time between 5 minutes and 500 hours in continuous manner or in time intervals.
• the transition metals and/or transition metal compounds are selected from the group of the transition metals acting as catalysts or from the group of the elements forming carbonyl complexes.
• Transition metal compounds according to the invention are in particular also obtained if transition metals forming carbonyl complexes and/or suitable as hydrogenating catalysts such as manganese, iron, cobalt, nickel, platinum are used individually or in mixture in the reaction mixture.
• the transition metals for example, nickel and/or cobalt and/or manganese and/or iron and/or platinum and/or niobium and/or iron and/or tungsten and/or tantalum and/or copper and/or zinc can be employed.
• the transition metals are employed in elemental form as a powder.
• cyanamide and/or ammonium dicyandiamide and/or dicyandiamide and/or melamine are employed as the slightly condensed C—N—H compounds.
• compounds are understood by non-condensed or slightly condensed C—N—H compounds, which result in precursors of the carbon nitride like melem in further condensation.
• cyanides and/or cyano complexes and/or isocyan complexes are added to the reaction mixture according to the invention consisting of non-condensed or slightly condensed C—N—H compounds and transition metals and/or transition metal compounds.
• boron powders and/or boron compounds such as for example lithium boride LiB 12 and/or other nitride forming elements and/or the compounds thereof are added to the reaction mixture according to the invention consisting of non-condensed or slightly condensed C—N—H compounds and transition metals and/or transition metal compounds before and/or after one or more heat treatments in the first temperature range.
• At least one further heat treatment in a second temperature range between 520° C. and 700° C. is effected.
• thermolysis of the transition metal compounds according to the invention the imino groups become available as a part of isocyan components for the formation of stable transition metal complexes.
• the characteristic of the transition metal compounds according to the invention to form materials with cubic lattice structure in the thermolysis is due to the presence of isocyan structures in the di-imino-tri-s-triazine molecule.
• the di-imino-tri-s-triazine transition metal compounds according to the invention have the excellent characteristic of converting themselves to material containing carbon and nitrogen with cubic lattice structure in the thermolysis. From the prior art, it is not known that by heat treatment of reaction mixtures consisting of for example cyanamide and/or dicyandiamide and/or melamine and one and/or more transition metals, reaction products are obtained, in which a C—N—H transition metal compound is present, which forms a material containing carbon, nitrogen and hydrogen, having cubic phases in further heat treatment.
• thermolysis product If the X-ray diffractograms of thermolysis products show the Bragg reflections of cubic carbon, thus, there is the evidence that a compound according to the invention has been subjected to the thermolysis.
• These compounds can—analogously to the compounds containing transition metal in the graphitic carbon nitride, Me-g-C3N4—be considered as compounds containing transition metal in the cubic carbon nitride, Me-c-C3N4.
• the transition metal compound according to the invention in the second temperature range between 520° C. and 700° C., for example, nickel transport in the gaseous phase can be observed.
• Transition metal compounds according to the invention having for example a crystal lattice analogous to the nickel carbide and subjected to the mentioned further heat treatment in the second temperature range, surprisingly transition to reaction products, which show Bragg reflections in the X-ray powder diagram, according to which materials are present in a cubic space group similar to the diamond.
• d-values have been determined: 2.045v, 1.774s, fluctuation range: ⁇ 0.01 (for comparison: cubic carbon d-values: 2.043vs, 1.769w, 1.251s).
• the further heat treatment in the second temperature range can be performed.
• Cubic boron nitride is formed from the reaction mixtures consisting of the transition metal compounds according to the invention and boron powder and/or boron compounds at heat treatment temperatures above 500° C. If Bragg reflections associated with the cubic boron nitride are found in the X-ray diffractogram of the reaction products from such heat treatments, thus, these Bragg reflections are an evidence of the presence of transition metal compounds according to the invention in the reaction mixture used for thermolysis.
• the second heat treatment can also be performed in one-stage or multi-stage manner or in alternating manner within the second temperature range.
• the second heat treatment is performed such that it encompasses the first and the second temperature range.
• the heat treatment within the second temperature range is performed over a period of time between 5 minutes and 500 hours in continuous manner or in time intervals.
• these transition metal compounds advantageously have a metal carbide structure.
• the transition metal compounds contain di-imino-tri-s-triazine as a component.
• transition metal compounds according to the invention can serve for the production of economically interesting valuable materials, in particular valuable materials containing carbon and nitrogen, having cubic phases.
• the transition metal compounds according to the invention have an X-ray diffractogram comparable to the transition metal carbide.
• the transition metal compounds according to the invention can for example have the following structural formulas: Me3C2HN(C6N9H4), Me6C4H2(C6N9H4)2 or Me3(C6N9H4)3.
• the transition metal compounds advantageously have a metal carbide structure.
• the transition metal compounds produced according to a method described above within the scope of a heat treatment in the first temperature range are used for producing materials containing carbon and/or nitrogen, present in the cubic crystal lattice.
• tetragonal isocyan transition metal (0) complexes for producing materials containing carbon and/or nitrogen, present in the cubic crystal lattice is also encompassed according to the invention.
• the transition metal compounds according to the invention and tetragonal tetraisocyan transition metal (0) compounds are usable as reactive templates for producing materials containing cubic carbide, nitride and/or carbonitride.
• An addition of compounds containing CN groups, such as for example cyanides and/or cyano complexes present in cubic lattice structure, to the reaction mixture according to the invention extends the possibilities of use of such reaction mixtures as reactive templates.
• the present invention provides access as simple as possible to the materials according to the invention.
• a crucial feature of the method according to the invention is the selection of the transition metals.
• the transition metals are for example selected from the group of the transition metals forming carbonyls.
• a further feature of the method according to the invention is the composition of the reaction mixture.
• the molar proportion of transition metal in the reaction mixture is at least 6 percent.
• reaction mixtures with a molar proportion of transition metal between 10 and 40 percent are employed.
• the reaction mixture can be subjected to the heat treatment as bulk material. With occurring melting phases, by suitable measures as shaking or stirring, demixing of the reaction partners is to be prevented.
• the heat treatment can be performed in one or more stages.
• the multi-stage heat treatment can additionally be composed of a pretreatment and one and/or more main treatments.
• the pretreatment in particular includes heating the reaction mixture to one and/or more pretreatment temperatures, dwelling at these pretreatment temperatures, cooling down, crushing and homogenizing the obtained pretreatment product.
• the pretreatment temperatures are preferably in the range between 150° C. and 400° C.
• pretreatment temperatures melting phases can basically occur, to which—depending on the composition of the reaction mixture—conversion reactions associated with severe gas emission can follow.
• the duration of dwelling is basically a non-crucial parameter. A dwelling time in the pretreatment between 10 min and a few hours is usual.
• a product is present, in which the transition metal can be present in a partially reacted form.
• the main treatment then includes heating the crushed and homogenized product obtained in the pretreatment and/or heating the starting reaction mixture to one and/or more main treatment temperatures, namely the first and/or the second temperature ranges, dwelling at these temperatures, cooling down to room temperature, crushing and homogenizing.
• the temperatures applied in the first heat treatment for producing the transition metal compound according to the invention are in the first temperature range between 150° C. and 570° C., in particular between 300° C. and 540° C. or between 400° C. and 550° C.
• the second heat treatment of the transition metal compound according to the invention is subjected to a second temperature range between 520° C. and 700° C., preferably between 550° C.
• the dwelling time is between a few minutes and several hours.
• a material is obtained, which has Bragg reflections similar to the cubic carbon in the X-ray powder diagram.
• an element forming nitride and/or carbide for example elemental boron and/or a boron compound
• the mixture is homogenized and is subjected to a further heat treatment in the temperature range from 500° C. to 700° C., in particular between 550° C. and 620° C.—at a dwelling time between a few minutes and several hours—then, a further reaction product is obtained, which has Bragg reflections for example similar to the cubic boron nitride in the X-ray powder diagram.
• Heat treatments of reaction mixtures containing C—N—H compounds and transition metals can be performed in normal containers of metal, glass or quartz glass suitable for the reaction. Volatile by-products arising in the heat treatment can preferably be separated in and/or after each treatment step, for example by escaping, by diffusing or absorbing.
• the heat treatment can be performed at negative pressure and/or normal pressure and/or at moderate overpressure and/or at high pressures generated by applying external pressure.
• the heat treatment can be performed with or without protective gas. Reaction products obtained from the heat treatment are preferably present as reproducible solids.
• the compounds and materials producible according to the method according to the invention can have further characteristics, which make their use advantageous in the most different fields, e.g. as catalysts in organic reactions, as solid electrolytes, as energy storages, sensors, semiconductors, fillers, grinding and polishing agents, ceramic and cermets.
• the characteristics of the materials according to the invention can be altered if further elements and/or their compounds, for example carbides, nitrides, borides, cyanides and/or cyano complexes, are added to the reaction mixture.
• the production and use of such metal containing materials in particular containing carbon and nitrogen, having cubic phases, which contain further elements, is also the subject matter of the present invention.
• a part of the heat treatment was performed under NH3 pressure.
• a compound is present, in which a (C6N9H4) residue is linked to a Me3 cluster via —N ⁇ CH—C.
• the compound has the structure: Ni3C2HN(C6N9H4) and can be represented as follows:
• a reaction mixture of nickel powder and dicyandiamide in the molar ratio of 1:2.15 was produced.
• the reaction mixture was filled into a glass reactor.
• the reactor was evacuated, the reaction mixture was heated to ca. 200-230° C., melting phase, shaking, low gas surge. Then, the reaction mixture was heated up to 520° C. during 20 minutes and kept at this temperature for 40 minutes. After cooling down, a brown reaction product was obtained. After crushing and homogenizing, the reaction product was subjected to elemental analysis without further conditioning.
• C—N—H—O combustion analysis provided the following values in percent by weight: carbon 22.6, nitrogen 29.8, hydrogen 1.14, oxygen 1.85 and nickel 44.61 (from difference to 100% by wt.).
• a transition metal compound was produced at a first heat treatment temperature of 400° C. and a treatment duration of 100 minutes.
• 0.5 g of this reaction product were placed in a glass reactor, the filled reactor was provided with an open capillary and introduced into a tube furnace.
• the reaction product thus introduced into the tube furnace was subjected to a second heat treatment temperature of 570° C.-580° C. with a dwelling time of 30 minutes.
• a grey-brown powder was obtained as the reaction product.
• the d-vales obtained by X-ray diffraction with a powder diffractometer of 2.054vs and 1.780s are very similar to the d-values of 2.043 and 1.769 known for the cubic carbon phase.
• a reaction mixture consisting of dicyandiamide, nickel powder and manganese powder in the molar ratio of 8:1:1 was treated according to the method described in example 1.
• 0.7 g of the homogenized reaction product/powder was subsequently intensively mixed with 0.15 g of amorphous boron powder and this mixture was introduced into a quartz glass reactor.
• the filled reactor equipped with a pressure regulating assembly was placed in a treatment furnace and subjected to a further heat treatment at a temperature of 580° C. with a dwelling time of 4.5 hours.
• a brown powder was obtained, characterized by the following d-values of the Bragg reflections: d-values: 2.089vs, 1.791s, 1.765w.
• Chemical formula NiC6N9H4; structural formula: Ni3(C6N9H4)3 (see also example 4; Me Ni).
• the di-imino-tri-s-triazine components can be recognized in the described structural formulas. If one considers the di-imino-tri-s-triazine molecule, thus, one recognizes that the imino groups are present as isocyan hydrogen components bound to nitrogen. These components result in the formation of transition metal isocyan complexes in the thermolysis of transition metal di-imino-tri-s-triazine compounds.
• a reaction mixture consisting of cyanamide, nickel powder, manganese powder, zinc cyanide powder and boron powder in the molar ratio of 2.8:1:1:1:6.3 was produced. 2.6 g of this mixture was filled into a nickel tube (internal diameter 6.0 mm), the tube was closed on both sides and introduced into a container with internal diameter of 12 mm. The space between container and tube was filled up with melamine, the container was closed and placed in a chamber furnace.
• a modified main treatment with a duration of 4 days was effected, wherein the furnace was kept at the following temperatures alternately of each 12 hours: 590, 540, 600, 560, 610, 540, 620, then 6 hours 630 and 9 hours 660° C.
• the reaction product 1.8 g of a black-brown powder was obtained, characterized by the following d-values of the Bragg reflections: 4.757s, 2.691s, 2.116vvs, 2.0351w, 1.835vs, 1.675s, 1.297s and 1.107s.
• the found d-values of 2.116vvs and 1.835vs and 1.297s show similarity with the Bragg reflections existing for cubic boron nitride of the X-ray powder diagram.
• the distance of the two reflections of 2.116 and 1.835 is 0.281, with c-BN, this value is at 0.274.
• the reaction product described in example 6 was obtained by heat treatment of a reaction mixture at atmospheric pressure.
• the elemental analysis yielded the chemical formula NiC6N9H4.
• the compound has a lattice analogous to the nickel carbide Ni3C, wherefore this compound is present in the structure of Ni3(C6N9H4)3.
• the corresponding structural formula Ni3(C6N9H4)3 can be taken from example 4.
• each one Ni atom of the Ni3 cluster is linked to each one di-imino-tri-s-triazine.
• this reaction product is identical with the approach described in example 6 concerning the reaction mixture, input amount and course of the procedure including the stage of the exothermic decomposition of dicyandiamide.
• the test tube was closed, it was placed in a chamber furnace preheated to ca. 560° C. After 45 minutes, the test tube was removed at a temperature of 555° C. 2.4 g of a brown-grey magnetic reaction product was obtained.
• the product shows the following Bragg reflections: 3.236s, 2.289w, 2.169w, 2.052vs, 2.025s, 1.776s, 1.256s (see figure 2).
• this transition metal compound is described in example 4. It is the first reaction product described there, in which dicyandiamide, nickel powder and manganese powder were converted in the molar ratio of 8:1:1 at 500° C. and a dwelling time of 60 minutes.
• the reaction product described in example 8 was placed about 10 mm high on the bottom of a quartz glass reactor disposed perpendicularly. A nickel tube immersing ca. 5 mm in this bulk was approximately centrally fixed in the reactor.
• the closed reactor equipped with pressure equalizing device was heated in a chamber furnace, flooded with ammonia at ca. 400° C., and at ca. 430° C. methane was introduced into the powder bulk through the nickel tube with a volumetric flow of one bubble per second.
• the temperature in the chamber furnace was raised from 430° C. to 575° C. during 30 minutes. After a dwelling time of 10 hours at 570° C. to 577° C., the furnace was turned off and the quartz glass reactor was removed from the furnace after a cooling phase of 4 hours.
• a black, loose, powdery coating On the exterior of the nickel tube, in a range up to ca. 50 mm above from the lower end of the nickel tube, a black, loose, powdery coating has deposited. The coating was carefully stripped off from the nickel tube exterior, wherein ca. 80 mg of a black powder was obtained, characterized by the following Bragg reflections: 3.330s, 2.056vs, 2.045vs, 2.027s, 1.774s, 1.256s.
• reaction product In the production of the reaction product described in example 8, a metal mixture consisting of 50% nickel and 50% manganese was reacted with dicyandiamide.
• the reaction product of example 8 contains a heteronuclear metal cluster corresponding to Me3(C6N9H4)3, a (tri-(di-imino-tri-s-triazine))-tri(nickel-manganese).
• the further processing of the reaction product produced in example 8 is described in example 4. Boron powder was admixed to the reaction product and this mixture was heat treated for 4.5 hours at a temperature of 580° C.
• thermolysis of the (tri-(di-imino-tri-s-triazine))-tri(nickel-manganese) compound described in example 8 in the presence of boron a material was obtained, the X-ray powder diagram of which shows the Bragg reflections characteristic to cubic boron nitride: 2.089vs, 1.791s. Comparative values for c-BN: 2.087vs, 1.807s.
• the reaction product of example 9 is a product separated from the gaseous phase.
• methane was flown through a nickel tube into a bulk consisting of the reaction product of example 8 at a temperature of 570° C.
• the reaction product was deposited as a loose coating on the nickel tube exterior above the powder bulk.
• the Bragg reflections of the product described in example 9 contain the reflections of carbon and nickel present in cubic modification.
• gaseous transition metal isocyan complexes can be plausibly explained in that isocyan components arising in the thermolysis of di-imino-tri-s-triazine molecules directly react with transition metal and/or a nickel carbin species Ni(CH)+ present from the methane dehydrogenation reacts with ammonia and transition metal.
• Reaction products containing di-imino-tri-s-triazine transition metal compound have the Bragg reflections for melem and metal carbide in the X-ray powder diagram, partially also the Bragg reflections of the corresponding metal nitrides.
• the production, the C, N, H values of the elemental analysis as well as the Bragg reflections of some of the examined reaction products are listed under examples.
• the examples 10 to 19 are a component of test series performed with slight alterations, wherefore the descriptions only differ in detail. In these test series, it was determined that reaction products were also obtained, in which cubic boron nitride is present accompanied by the carbide, boride, nitride, optionally also the carbodiimide of the employed transition metal (example 12).
• transition metal isocyan complexes occur in the thermolysis of the transition metal compounds according to the invention, the reaction of which with boron results in cubic boron nitride, is comprehended in the conversion of tetra(phenylisocyanide)nickel(0) with boron to cubic boron nitride described in example 20.
• the d-values characteristic to cubic boron nitride prove that a compound according to the invention of the composition of CoC6N9H4 was formed in the heat treatment (520° C./1.5 h) of a reaction mixture consisting of cobalt powder and dicyandiamide in molar ratio of 1:4.

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